EP1685192B1 - Composition de resine pour marquage au laser - Google Patents

Composition de resine pour marquage au laser Download PDF

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Publication number
EP1685192B1
EP1685192B1 EP04819015A EP04819015A EP1685192B1 EP 1685192 B1 EP1685192 B1 EP 1685192B1 EP 04819015 A EP04819015 A EP 04819015A EP 04819015 A EP04819015 A EP 04819015A EP 1685192 B1 EP1685192 B1 EP 1685192B1
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EP
European Patent Office
Prior art keywords
weight
parts
rubber
resin composition
laser marking
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EP04819015A
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German (de)
English (en)
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EP1685192A1 (fr
EP1685192A4 (fr
Inventor
Seung-Cheol Ryoo
Bob Ryu
Lambert Park
Bong-Hyun Park
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020040068010A external-priority patent/KR100585280B1/ko
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Publication of EP1685192A4 publication Critical patent/EP1685192A4/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/02—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to elastomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • the present invention relates to a resin composition for laser marking, and more particularly, to a resin composition for laser marking, which has high contrast and excellent chemical resistance and is capable of easily adjusting transparency of finished products in marking white characters or marks using a laser beam.
  • Another way to mark characters or marks on a surface of a plastic product is a compressed labeling method.
  • this method is dsadvantageous in that the marked characters or marks are not permanent.
  • a method of marking characters or marks on a surface of a plastic product using a laser beam has recently been widely used, which is called a laser marking method.
  • the laser marking method is widely employed owing to its various advantages. That is, according to this method, characters or marks are designed using a computer, or, if necessary, the design of the characters or marks can be easily changed, fast and efficient marking is enabled, and elaborately, uniformly marked products can be produced. Also, even unskilled workers can perform the marking work without defects. Further, since this laser marking method is carried out in a non-contact type, it allows characters or marks to be easily marked even on an irregular surface. Since a solvent is not used, problems of environmental contamination or toxicity are not caused. Another advantage is that materials are recyclable. Thus, applications of such laser marking technique are rapidly growing.
  • the surface of a marked product made of a resin is foamed at a temperature of drectly below a melting point by absorbing a laser beam energy, a laser-irradated portion is evaporated to be engraved, or an instantaneous chemical change occurs on a marked surface for color change and blenching.
  • the white color of the marked characters or signs may not be vivid due to deposit of carbon residues or oxidzed materials produced by excess laser beam energy during the laser marking process.
  • chemical cranks may be easily caused to the surface of the marked product. For example, when a component product of a refrigerator contacts a foaming agent during foaming process, or when an injection molded product is contaminated, an organic solvent is used for cleaning the product, so that chemical resistance of the product becomes a critically important issue.
  • Japanese Patent Laid-open Publication No. 2001-302922 discloses a resin composition for laser marking comprising an ABS resin, maleimide-based copolymer, cyanided vinyl copolymer, ferric oxide as a black pigment, and other coloring agent.
  • the disclosed resin composition is used in laser marking, the white color of a marked product is not dstinct, which is due to deposition of carbon residue on a surface of the marked product, undesirably resulting in yellowish.
  • Japanese Patent Laid-open Publication No. 2000-212451 describes a method of marking white characters or marks on a bleak Background using a composition prepared by blending a PMMA resin and an ABS resin in a predetermined mixing ratio, and addng metal stearate, carbon black and titanium oxide.
  • a composition prepared by blending a PMMA resin and an ABS resin in a predetermined mixing ratio and addng metal stearate, carbon black and titanium oxide.
  • the whiteness of a marked product is not satisfactorily dstinct.
  • Japanese Patent Laid-open Publication No. 2001-139758 discloses a method of laser marking using at least one compound selected from the group consisting of acrylate ester, aromatic vinyl compound, cyanided vinyl compound and maleimide, an ethylene-(meth)acrylate ester-carbon monoxide-based ternary copolymer resin, carbon black, ferric oxide, triiron tetroxide, or titanium black as a black pigment, in the presence of a rubber polymer.
  • acrylate ester aromatic vinyl compound, cyanided vinyl compound and maleimide
  • an ethylene-(meth)acrylate ester-carbon monoxide-based ternary copolymer resin carbon black, ferric oxide, triiron tetroxide, or titanium black as a black pigment
  • JP 2000-129070 discloses a thermoplastic resin composition for laser marking prepared by blending thermoplastic resin containing rubber-reinforced resin, rubber free polymer, (meth)acrylic ester based polymer, carbon black, and dye.
  • KR 2003-0056479 discloses a thermoplastic resin composition for laser marking comprising rubbery polymer which contains small diameter and large diameter rubber particles, monomer mixture, molecular weight modifier, colouring pigment, and silicate compound.
  • US 2001-051688A discloses a butadiene-based rubber-reinforced resin produced by graft-polymerizing monomer components in the presence of particles of a butadiene-based rubber, said butadiene-based rubber-reinforced resin comprising a rubber phase containing particles having a small diameter particle and large diameter particle.
  • thermoplastic resin composition for laser marking capable of developing chromatic colours, comprising: a thermoplastic resin contains a rubber-reinforced resin obtained by polymerising at least one monomer in the presence of a rubber-like polymer and a polymer obtained by polymerising at least one monomer, wherein the rubber-like polymer is a mixture of at least two rubber-like polymers differing in particle size; at least one black system compound; and organic pigment.
  • DATABASE WPI Week 200411 Derwent Publications Ltd., London, GB; AN 2004-102516 XP002425543-& JP-A-2003 176396 discloses a laser-marking material which comprises a resin component which is a rubber reinforced vinyl-type resin obtained by graft copolymerising an aromatic vinyl monomer, a vinyl cyanide monomer, a meth(acrylic) acid ester monomer in the presence of rubber.
  • the composition further comprises relevant dyes/pigments in relevant quantities.
  • the present invention provides a resin composition for laser marking, which readily adjusts degree of transparency when marking white characters or marks using a laser beam, and offers superb whiteness of the marked white characters or marks and excellent chemical resistance.
  • a resin composition for laser marking comprising 0.0005 ⁇ 0.5 parts by weight of a black pigment, a black dye, or a mixture thereof; and 0.0001 ⁇ 0.5 parts by weight of a blue dye, a blue pigment, or a mixture thereof based on 100 parts by weight of a transparent resin composition comprising 80 ⁇ 99 wt% of a rubber quarternary transparent copolymer composition having aromatic vinyl compound, alkyl(meth)acrylate ester, and a vinyl cyan compound grafted to a mixture of a rubber polymer consisting of a small diameter polybutadiene rubber latex and a large diameter polybutadiene rubber latex, or a rubber quartenary transparent copolymer consisting of a large diameter polybutadiene rubber latex only, and 1 ⁇ 20 wt% of a thermoplastic urethane elastomer or a thermoplastic amide elastomer, wherein a difference in the refractive index between the thermoplastic
  • the rubber quarternary transparent copolymer composition contains 3 ⁇ 15 parts by weight of a small diameter polybutadiene rubber latex, 5 ⁇ 25 parts by weight of a large diameter polybutadiene rubber latex, 5 ⁇ 30 parts by weight of an aromatic vinyl compound, 40 ⁇ 70 parts by weight of alkyl(meth)acrylate ester, and 1 ⁇ 20 parts by weight of a vinyl cyan compound.
  • the content of the black pigment, the black dye or mixtures thereof is preferably in a range of 0.0005 ⁇ 0.03 parts by weight.
  • the gel content of the both latexes is in a range of 70 ⁇ 95% and the swelling index is in a range of 12 ⁇ 30.
  • rubber content in the rubber quarternary transparent copolymer having refractive index in a range of 1.508 ⁇ 1.528 is preferably in a range of 5 ⁇ 25 parts by weight.
  • the black pigment has a particle dameter in a range of 17 ⁇ 40 nm.
  • the blue dye is preferably an anthraquinone-based dye
  • the blue pigment may be one selected from the group consisting of phthalocyanine-based, cobalt blue-based, and ultramarine-based pigments.
  • a resin composition for laser marking according to the present invention comprises (C) 0.0005 ⁇ 0.5 parts by weight of a black pigment, a black dye, or a mixture of these compounds for absorbing laser light; and (D) 0.0001 ⁇ 0.5 parts by weight of a blue dye, a blue pigment, or a mixture of these compounds for enhancing the whiteness of a marked character or sign, based on 100 parts by weight of a transparent resin composition[(A)+(B)] comprising (A) 80 ⁇ 99 wt% of a rubber quarternary transparent copolymer composition having aromatic vinyl compound, alkyl (meth)acrylate ester, and a vinyl cyan compound grafted to a mixture of a rubber polymer consisting of a small dameter polybutadiene rubber latex and a large diameter polybutadiene rubber latex, or a rubber quarternary transparent copolymer consisting of a large diameter polybutadene rubber latex only, the copolymer having excellent impact resistance, chemical resistance and processability, and (B)
  • a preparation method of the rubber quarternary transparent copolymer comprises (a) preparing a small diameter polybutadiene rubber latex having an average particle dameter of 600 to 1500 ⁇ , a gel content of 70 to 95%, and a swelling index of 12 to 30 by reacting butadene at 55 to 70°C using a polymerization initiator, (b) preparing a large dameter polybutadiene rubber latex having an average particle dameter of 2600 to 5000 ⁇ , a gel content of 70 to 95%, and a swelling index of 12 to 30 by increasing the particle size of the small dameter polybutadene rubber latex, and (c) continuously or partially addng 3 to 15 parts by weight of the small dameter polybutadene rubber latex prepared in step (a), 5 to 25 parts by weight of the large dameter polybutadiene rubber latex prepared in step (b), 15 to 30 parts by weight of an aromatic vinyl oompound, 40 to 70 parts by weight of a alkyl (meth)acrylate ester compound, and 1 to 20
  • the particle dameter and gel content of the polybutadene rubber latex used in the present invention have a great influence on physical properties, includng transparency and impact strength, of a product, it is quite important to select appropriate mixing ratio of the small dameter polybutadene rubber latex and the large diameter polybutadene rubber latex when using rubber quarternary transparent copolymer composition instead of the large dameter polybutadene rubber latex.
  • the particle dameter of the rubber latex is smaller, the transparency of the product is enhanced and the impact strength and flowability deteriorate. As the particle dameter increases, the impact strength becomes higher and the transparency is lowered.
  • the refractive index of a mixture of monomers used in the present invention has an absolutely great influence on the transparency, and is adjusted by amounts of the monomers used and a mixing ratio thereof.
  • the overall refractive index of grafted ingredents should have a refractive index substantially the same with that of polybutadiene, that is, approximately 1.518.
  • the refractive index of styrene is approximately 1.59
  • the refractive index of methyl methacrylate is approximately 1.49
  • the refractive index of acrylonitrile is approximately 1.518.
  • a polybutadene rubber component is mainly used to increase the impact strength of a product, and is preferably contained in an amount of 5 to 25 parts by weight based on the total amount of the rubber quarternary transparent copolymer. If the amount of the polybutadene rubber component is less than 5 parts by weight, it is quite difficult to achieve a satisfactory impact strength. If the amount of the polybutadene rubber component is greater than 25 parts by weight, the excess gives rise to a reduction in the mechanical strength.
  • the aromatic vinyl compound serves primarily to enhance processability, and presumably serves in part to supply some of energy enabling an irradated portion to be fused and swollen by absorbing laser light energy in cooperation with a dye or pigment capable of fusing a laser beam.
  • the content of the aromatic vinyl compound used is adjusted within a range of 15 to 30 parts by weight based on the total weight of the rubber transparent quarternary copolymer for the refractive index of the rubber quarternary transparent copolymer to be 1.518.
  • the alkyl (meth)acrylate ester compound tends to absorb a relatively small amount of laser light, and is likely to foam rather than to be engraved, thereby enhancing a light dffusion effect and ultimately increasing the whiteness of the marked character or mark. Further, use of the alkyl (meth)acrylate ester compound makes materials experience less deterioration during laser irradation, and enhances weatherability of final products.
  • the vinyl cyan compound increases chemical resistance.
  • the amount of the vinyl cyan compound used is preferably in a range of 1 to 20 parts by weight based on the total weight of the rubber quarternary transparent copolymer. If the amount of the vinyl cyan compound used is less than 1 parts by weight, the chemical resistance of the resin composition of the present invention, thus the final prouct, deteriorates considerably. If the amount of the vinyl cyan compound used is greater than 20 parts by weight, the prepared polymer has a relatively strong yellowish tint, thereby deteriorating the visibility of the marked character or mark after the laser marking.
  • the various components may be added to a reactor in a lump method, in a multiple-step addng method, or in a continuously addng method.
  • a combination of the lump adding method and the continuously adding method is adjustably employed.
  • 100 parts by weight of 1,3-butadene, 1 to 4 parts by weight of emulsifier, 0.1 to 0.6 parts by weight of a polymerization initiator, 0.1 to 1.0 parts by weight of an electrolyte, 0.1 to 0.5 parts by weight of a molecular weight controlling agent and 90 to 130 parts by weight of dstilled water are add in a lump to a reactor for reaction at 50 to 65 °C for about 7 to about 12 hours.
  • 0.05 to 1.2 parts by weight of a molecular weight controlling agent is additionally added in a lump for reaction at 55 to 70 °C for about 5 to about 15 hours, thereby yieldng small dameter polybutadene rubber latex having an average particle diameter of 600 ⁇ to 1500 ⁇ and a gel content of 70 % to 95 %, and a swelling index of 12 to 30.
  • Examples of the emulsifier useful in the present invention include alkylaryl sulfonate, alkali methyl alkyl sulfate, sulfonated alkyl ester, fatty acid soap, alkali metal salts of rosin acid, and the like, which may be used singly or in a combination of at least two compounds.
  • the polymerization initiator may be a water-soluble persulfate compound or peroxy compound, and a redox initiator system can be used as the initiator.
  • Preferred examples of the water-soluble persulfate soluble compound include a sodum persulfate compound, potassium persulfate compound and the like.
  • peroxy compound initiator examples include cumene hydroperoxide, diisopropyl benzenehydroperoxide, tertiary butyl hydroperoxide, p-methane hydroperoxide, benzoylperoxide, and the like, which a re used singly or in a combination of at least two compounds.
  • a zobisisobutyronitrile (AIBN) may be used.
  • Examples of the electrolyte useful in the present invention include KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7, K 3 PO 4 , Na 3 PO 4 , K 2 HPO 4 , Na 2 HPO 4 , and the like. These compounds can be used singly or in a combination of at least two compounds.
  • Preferred examples of the molecular weight controlling agent include mercaptans, and the like.
  • aqueous acetic acid solution 3 to 4 parts by weight of an aqueous acetic acid solution was slowly added to 100 parts by weight of small diameter rubber latex having a particle diameter of 600 ⁇ to 1500 ⁇ , a gel content of 70 % to 95 % and a swelling index of 12 to 30 to make particles bulky with stirring, and stopped stirring to prepare large dameter rubber latex having a particle diameter of 2600 ⁇ to 5000 ⁇ , a gel content of 70 % to 95 % and a swelling index of 12 to 30.
  • the large dameter rubber latex used to impart impact resistance may also be prepared by a drect polymerization method. However, the polymerization method requires a long reaction time and is limited in yieldng large dameter rubber latex having a high gel content.
  • small dameter rubber latex having a high gel content is first prepared and large dameter rubber latex is then prepared by making particles of the small dameter rubber latex bulky by addng an acidic material to the small dameter rubber latex.
  • the graft copolymerization is preferably performed at 65 °C to 80 °C for about 4 to about 7 hours.
  • usable examples of the alkyl (meth)acrylate ester compound useful include methyl methacrylate, methyl acrylate, and the like
  • usable examples of the aromatic vinyl compound include styrene, ⁇ -methylstyrene, o-ethylstyrene, p-ethylstyrene, vinyl toluene, and the like
  • usable examples of the vinyl cyan compound include acrylonitrile, methacrylonitrile, ⁇ -ethylacrylonitrile, and the like.
  • Examples of the emulsifier useful in the polymerization include alkyl aryl sulfonate, alkali metal sulfate, sulfonated alkyl ester, fatty add soap, alkali metal salts of rosin acid, and the like, which can be used alone or as a mixture of more than two kinds.
  • Representative examples of the molecular weight controllig agent include tert-didecylmercaptan and the like.
  • polymerization initiator examples include redox catalyst system compounds composed of peroxides such as cumene hydro peroxide, diisopropyl benzene hydroperoxide, or a persulfate compound, and reducing agents such as sodum formaldehyde sulfoxylate, sodum ethylene damine tetraacetate, ferrous sulfate, dextrose, sodum pyrrolinate, or sodum sulfite.
  • a polymerization conversion ratio of the latex acquired after polymerization is not less than 98%.
  • the latex is coagulated using aqueous calcium chloride solution, followed by dehydrating and drying, thereby obtaining rubber quarternary transparent copolymer powder.
  • thermoplastic elastomer is used to enhance chemical resistance against various solvents used in intermedate processes, such as foaming, cleansing agents used for removing contaminants after injection moldng, or solvents which final products may contact during actual use.
  • the thermoplastic elastomer is also used to assist various inorganic addtives added to facilitate foaming during laser marking to be dspersed and to prevent the inorganic additive from impairing the impact strength of the resin composition for laser marking.
  • the laser marking resin is prepared using only the rubber quarternary transparent copolymer, it has good laser markability but poor chemical resistance, so that chemical cracks may be generated due to various chemicals which may be contracted during intermedate processes or actual use.
  • the thermoplastic elastomer is used to improve the chemical resistance of the rubber quarternary transparent copolymer without impairing the transparency thereof.
  • the rubber quaternary transparent polymer of the thermoplastic urethane elastomer or thermoplastic amide elastomer has good compatibility owing to the interactions, e.g., a secondary polar bondng, between an amide group in the thermoplastic urethane elastomer or the thermoplastic amide elastomer and a carboxyl group in the rubber quarternary transparent copolymer.
  • interaction between an alkyl ether group and a styrene group in the elastomer improves compatibility of the elastomers.
  • thermoplastic urethane elastomer or the thermoplastic amide elastomer is similar to that of the rubber quarternary transparent copolymer, the overall transparency of the blend composition can be maintained by the interaction therebetween.
  • thermoplastic urethane elastomer In the case of forming an opaque laser marking product, it is not necessary to consider the refractive index of the thermoplastic elastomer. In the case of forming a semi-transparent laser marking product, it is preferable that a difference in the refractive index between the thermoplastic urethane elastomer or the thermoplastic amide elastomer and the rubber quarternary transparent copolymer is not greater than 0.01. If the difference in the refractive index between the thermoplastic urethane elastomer or the thermoplastic amide elastomer and the rubber quarternary transparent copolymer is greater than 0.01, as the amount of the thermoplastic elastomer used increases, the transparency of the resin composition, thus the final product tend to deteriorate.
  • thermoplastic urethane elastomer or the thermoplastic amide elastomer is highly hydrophilic, the final product does not adsorb dust during actual use and improves low-temperature impact resistance and degree of elongation.
  • a black pigment, a bleak dye, or a mixture thereof provides energy needed to cause polymeric molecular chains to swell by absorbing laser beam energy, and is dsoolored by being oxidized, thereby rendering white characters or marks to be visible to human eyes.
  • the properties and amounts of these materials used have a great influence on whiteness and/or visibility of the characters or marks.
  • the black pigment is excessively used, several adverse effects may be exhibited, though it can be laser marked with a lesser amount of laser beam energy. That is, excessive oxidation residues may be created, some of unoxidzed black pigments may remain on the background color, engraving may overwhelm foaming due to excessive energy supplied, and a surface of the marked product may become messy due to overly facilitated oxidation and carbonization of the resin composition. Conversely, if the amount of the black pigment is too small, the energy supplied to the marking surface is not enough to make the polymer molecular chains difficult to swell, and the laser beam energy required for laser marking increases, so that the marked surface may have a yellowish tint or laser marking performance may become poor. In the case of producing a semi-transparent marking product, the black pigment or the bleak dye is used in a limited amount to maintain the transparency, demanding for increased laser beam energy for marking.
  • Carbon black used as a black pigment preferably has a particle dameter in a range of 17 to 40 nm, and is preferably contained in an amount of 0.0005 to 0.5 parts by weight. If the particle dameter of the black pigment is less than 17 nm, a large amount of energy is consumed. If the particle dameter of the black pigment is greater than 40 nm, the tensile strength and impact strength may deteriorate. The amount of the black pigment used depends upon whether a product to be laser marked is necessarily opaque or transparent.
  • the black pigment is preferably used in an amount of 0.02 to 0.5 parts by weight based on 100 parts by weight of the transparent resin composition (A+B), dependng on a tone of a background color. If the amount of the black pigment used is less than 0.02 parts by weight, the product becomes transparent.
  • titanium oxide or other inorganic fillers may be added, which may, however, result in lowering of blackness.
  • the background color is bleak or blue, a small amount of carbon black is generally used, and when white marking on a gray background is intended to achieve, titanium oxide is typically used, requiring a large amount of a black pigment.
  • 0.0005 to 0.03 parts by weight of carbon black is preferably used from the viewpoint of transparency.
  • the carbon black may be used in combination of a black dye, if necessary.
  • a laser marking work is performed with increased laser power due to a limited amount of carbon black capable of absorbing energy. If the amount of carbon black is less than 0.0005 parts by weight, the amount of laser beam energy absorbed is too small to properly achieve marking of characters or marks on the transparent or semi-transparent product. If the laser power is overly increased to perform marking, however, irradation of a laser beam with high energy may cause some ingredents of the composition to be carbonized, which is undesirable. If the amount of carbon black is greater than 0.03 parts by weight, the transparency is considerably deteriorated, making it difficult to produce transparent or semi-transparent products.
  • a black dye is typically used.
  • the transparency is adjusted in a limited manner.
  • the black dye having good dspersability is used in combination with carbon black.
  • the amount of the black dye used is preferably in a range of 0.0001 to 0.1 parts by weight.
  • dyes having various colors may also be used in combination with the black dye.
  • a blue dye, a blue pigment, or a mixture thereof are used to improve whiteness and visibility of characters or marks to be marked.
  • the blue dye or the blue pigment removes a yellowish tint produced when a surface of a laser marked product is partially oxidzed due to energy absorbed during laser marking, thereby further enhancing whiteness of the characters or marks.
  • substance capable of absorbing laser beam energy exists in a small quantity, like in a transparent or semi-transparent product, it is necessary to increase the intensity of laser beam irradation, the product is vulnerable to oxidation.
  • dstinctly visible white characters or marks can be marked by adjusting the amount of the blue dye or the blue pigment according to the extend of oxidation.
  • blue dye useful in the present invention examples include anthraquinone based dyes, and examples of the blue pigment include phthalocyanine based pigments, cobalt blue based pigments, ultramarine based pigments, and the like.
  • the blue dye or the blue pigment as an addtive for enhancing whiteness is preferably used in an amount of 0.0001 to 0.5 parts by weight.
  • the resin composition for laser marking according to the present invention may further include titanium oxide, which serves to facilitate foaming of the resin during laser beam irradiation.
  • titanium oxide is used for the purposes of adjusting light transmittance or improving the whiteness of a marked portion during laser marking. If the particle size of titanium oxide becomes large, the titanium oxide imparts a yellowish tint to the characters or marks to be laser marked, while exhibiting good light shieldng capability. If the particle size of titanium oxide becomes small, the characters or marks to be laser marked will have a slightly bluish tint, increasing the visibility of the marked characters or marks.
  • various inorganic addtives e.g., talc, as well as titanium oxide may be used.
  • the inorganic addtives are not dspersed properly, a surface of the marked product becomes uneven.
  • a master batch is preferably used.
  • Use of the inorganic addtive may deteriorate impact strength of the product.
  • the composition according to the present invention includes thermoplastic urethane elastomer or thermoplastic amide elastomer, deterioration of impact strength can be reduced and the inorganic addtive can be effectively dspersed.
  • All the above-described components including the rubber quarternary transparent copolymer powder, the thermoplastic elastomer, the black pigment, the black dye, the blue dye, the blue pigment, and so on, are mixed together and extruded at a temperature of about 180°C to about 230°C, thereby preparing the resin composition for laser marking according to the present invention in the form of a master batch pellet.
  • an antioxidant, a thermal stabilizer, lubricant, a weatherability enhancer, an antistatic agent, an antifungal agent, and the like may be added if necessary. In addtion, other colorants for adjusting colors may be optionally added.
  • distilled water 100 parts by weight of 1,3-butadiene as a monomer, 1.2 parts by weight of potassium rosinate as an emulsifier, 1.5 parts by weight of potassium oleate, 0.1 parts by weight of Na 2 CO 3 as an electrolyte, 0.5 parts by weight of KHCO 3 , and 0.3 parts by weight of tert-dodecyl mercaptan (TDDM) as a molecular weight controlling agent were placed together in a lump in a nitrogen-substituted polymerization reactor (autoclave).
  • TDDM tert-dodecyl mercaptan
  • reaction temperature was raised to 55°C, and then the reaction was initialized by addng in a lump 0.3 parts by weight of potassium sulfite as an initiator to the reactor, and reacted for 10 hrs. Thereafter, 0.05 parts by weight of TDDM was further added to the reactor, and then the reaction was completed by reacting for 8 hrs at 65°C.
  • rubber latex having a particle diameter of 1000 ⁇ , a gel content of 90 %, and a swelling index of 18.
  • reaction temperature was raised up to 73 °C over 2 hours.
  • the polymerization conversion rate was approximately 99.5 %, and the solid type coagulate content was 0.1%.
  • This latex was solidified with aqueous solution of calcium chloride, and washed, yielding powder, which is called a rubber quarternary transparent copolymer A1.
  • reaction temperature was raised up to 73 °C over 2 hours.
  • the polymerization conversion rate was approximately 99.8 %, and the solid type coagulate content was 0.12%.
  • This latex was solidfied with aqueous solution of calcium chloride, and washed, yieldng powder, which is called a rubber quarternary transparent copolymer A2.
  • the polymerization conversion rate was approximately 99.2 %, and the solid type coagulate content was 0.3%.
  • This latex was solidfied with aqueous solution of calcium chloride, and washed, yieldng powder, which is called a rubber quarternary transparent copolymer A3.
  • the prepared plate-shaped samples were laser marked using a Nd:YAG laser marking machine (Model name: SY-2000) manufactured by EO Technique Co., Ltd. under the conditions of 1064 nm in wavelength, 5 kHz in vibration frequency, 3 Watt in laser power.
  • a notch was formed on a 1/8 inch sample and the impact strength was measured as per ASTM D256 using an Izod impact strength tester.
  • the degree of transparency was measured as per ASTM D 1003.
  • the refractive index was measured as per ASTM D 542.
  • the markability was evaluated through observation by naked eye.
  • A2 18 wt% in rubber content, 1.518 in refractive index
  • A3 23 wt% in rubber content, 1.518 in refractive index
  • thermoplastic urethane elastomer having a refractive index of 1.518 K470A manufactured by Kolon Chemical Co., Ltd.
  • thermoplastic urethane elastomer having a refractive index of 1.525 (K285PCAT manufactured by Kolon Chemical Co., Ltd.);
  • thermoplastic amide elastomer having a refractive index of 1.51 (Pelestat NO6321 manufactured by Sanyo Chemical Ind.);
  • Carbon black Pigment Black 07 manufactured by Nippi Korea;
  • Black dye Diaresin Black B manufactured by Mitsubishi Chemical Corp.
  • Blue dye Macrolex Blue 3R manufactured by Bayer Corp.
  • Blue pigment Ultramarine Blue 05 manufactured by Holiday Corporation.
  • PMMA IF-850 manufactured by LG Chemical Co., Ltd.
  • the marked product produced using the resin composition for laser marking according to the present invention has high chemical resistance.
  • the use of the resin composition for laser marking allows for achievement of highly visible white markings without a yellowish tint and easily adjustable transparency of the marked product.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

L'invention concerne une composition de résine destinée au marquage au laser, qui comprend 0,0005 à 0,5 parts en poids d'un pigment noir, d'un colorant noir ou un mélange des deux, et 0,0001 à 0,5 parts en poids d'un colorant bleu, d'un pigment bleu ou un mélange des deux sur la base de 100 parts en poids d'une composition de résine transparente comprenant 80 à 99 % en poids d'une composition copolymère transparente quaternaire de caoutchouc ou d'un copolymère transparent quaternaire de caoutchouc, et 1 à 20 % en poids d'un élastomère d'uréthane thermoplastique ou élastomère d'amide thermoplastique. Un marquage au laser, produit au moyen de la composition de résine pour marquage au laser, présente une résistance chimique élevée. En outre, l'utilisation de cette composition permet de réaliser des marquages blancs particulièrement visibles sans teinte jaunâtre et une transparence facilement réglable du produit marqué.

Claims (7)

  1. Composition de résine pour un marquage au laser comprenant :
    de 0,0005 à 0,5 partie en poids d'un pigment noir, d'un colorant noir ou d'un mélange de ceux-ci ; et
    de 0,0001 à 0,5 partie en poids d'un colorant bleu, d'un pigment bleu ou d'un mélange de ceux-ci, rapporté à 100 parties en poids d'une composition de résine transparente comprenant 80-99 % en poids d'une composition de copolymère transparent quaternaire de caoutchouc présentant un composé vinylique aromatique, un ester de (méth)acrylate d'alkyle et un composé vinylcyano greffé sur un mélange d'un polymère de caoutchouc constitué d'un latex de caoutchouc de polybutadiène de petit diamètre et d'un latex de caoutchouc de polybutadiène de grand diamètre, ou d'un copolymère transparent quaternaire de caoutchouc constitué d'un latex de caoutchouc de polybutadiène de grand diamètre uniquement et de 1 à 20 % en poids d'un élastomère d'uréthane thermoplastique ou d'un élastomère d'amide thermoplastique,
    dans laquelle une différence de l'indice de réfraction entre l'élastomère d'uréthane thermoplastique ou l'élastomère d'amide thermoplastique et le copolymère transparent quaternaire de caoutchouc est d'au plus 0,01,
    dans laquelle le latex de caoutchouc de polybutadiène de petit diamètre présente un diamètre moyen de particules de 600 à 1 500 Å, le latex de caoutchouc de polybutadiène de grand diamètre présente un diamètre moyen de 2 600 à 5 000 Å.
  2. Composition de résine pour un marquage au laser selon la revendication 1, dans laquelle la composition de copolymère transparent quaternaire de caoutchouc contient de 3 à 15 parties en poids d'un latex de caoutchouc de polybutadiène de petit diamètre, de 5 à 25 parties en poids d'un latex de caoutchouc de polybutadiène de grand diamètre, de 5 à 30 parties en poids d'un composé vinylique aromatique, de 40 à 70 parties en poids d'ester de (méth)acrylate d'alkyle et de 1 à 20 parties en poids d'un composé vinylcyano.
  3. Composition de résine pour un marquage au laser selon la revendication 1, dans laquelle lorsque la composition selon la présente invention est appliquée sur des produits semi-transparents, la teneur en le pigment noir ou en colorant noir se trouve dans un intervalle de 0,0005 à 0,03 partie en poids.
  4. Composition de résine pour un marquage au laser selon la revendication 1, dans laquelle la teneur en gel des deux latex se trouve dans un intervalle de 70 à 95 % et l'indice de gonflement se trouve dans un intervalle de 12 à 30.
  5. Composition de résine pour un marquage au laser selon la revendication 1, dans laquelle la composition de copolymère transparent quaternaire de caoutchouc peut comprendre du caoutchouc contenu dans une quantité de 5 à 25 parties en poids et ayant un indice de réfraction de 1,508 à 1,528.
  6. Composition de résine pour un marquage au laser selon la revendication 1, dans laquelle le pigment noir présente un diamètre de particules dans un intervalle de 17 à 40 nm.
  7. Composition de résine pour un marquage au laser selon la revendication 1, dans laquelle le colorant bleu est un colorant à base d'anthraquinone et le pigment bleu peut être un pigment choisi dans le groupe constitué des pigments à base de phtalocyanine, à base de bleu de cobalt et à base de bleu d'outremer.
EP04819015A 2003-11-19 2004-11-09 Composition de resine pour marquage au laser Active EP1685192B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR20030082342 2003-11-19
KR1020040068010A KR100585280B1 (ko) 2003-11-19 2004-08-27 레이저 마킹용 수지 조성물
PCT/KR2004/002892 WO2005049727A1 (fr) 2003-11-19 2004-11-09 Composition de resine pour marquage au laser

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EP1685192A1 EP1685192A1 (fr) 2006-08-02
EP1685192A4 EP1685192A4 (fr) 2007-05-02
EP1685192B1 true EP1685192B1 (fr) 2010-02-17

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US (1) US20050137296A1 (fr)
EP (1) EP1685192B1 (fr)
CN (1) CN1284825C (fr)
DE (1) DE602004025605D1 (fr)
WO (1) WO2005049727A1 (fr)

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CN100567016C (zh) * 2005-02-21 2009-12-09 大科能树脂有限公司 激光标记用叠层体
WO2014062601A1 (fr) * 2012-10-16 2014-04-24 Arkema France Compositions thermoplastiques transparentes résistantes au choc
WO2015036526A1 (fr) 2013-09-16 2015-03-19 Styrolution Group Gmbh Matières à mouler thermoplastiques noir foncé à brillance élevée et leur production
CN104448531B (zh) * 2014-12-29 2016-08-24 金发科技股份有限公司 一种用于浅色标识的镭雕母粒及其制备方法和应用
JP6440531B2 (ja) * 2015-03-05 2018-12-19 キヤノン株式会社 電子写真用部材、及び、その製造方法
KR101905939B1 (ko) 2015-08-31 2018-10-08 주식회사 엘지화학 열가소성 수지 조성물 및 이의 제조방법
CN115516018A (zh) 2020-04-02 2022-12-23 英力士苯领集团股份公司 高暗度和高光泽度尺寸稳定的热塑性smma成型组合物
CN112226008B (zh) * 2020-10-20 2023-04-18 上海金发科技发展有限公司 一种可形成白色镭雕图纹的组合物
CN112521729B (zh) * 2020-11-12 2023-04-18 上海金发科技发展有限公司 一种高流动性的黑色阻燃增强聚对苯二甲酸乙二醇酯组合物及其制备方法
CN117999314A (zh) 2021-09-14 2024-05-07 英力士苯领集团股份公司 透光率增加的asa-共聚物组合物及其制备方法
CN114656743B (zh) * 2021-12-28 2024-01-09 上海普利特复合材料股份有限公司 一种颜色标识可选的激光镭雕母粒及其制备方法

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DE602004025605D1 (de) 2010-04-01
EP1685192A1 (fr) 2006-08-02
EP1685192A4 (fr) 2007-05-02
WO2005049727A1 (fr) 2005-06-02
US20050137296A1 (en) 2005-06-23
CN1284825C (zh) 2006-11-15
CN1626576A (zh) 2005-06-15

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